Process for subbing photographic polyester films

ABSTRACT

The present invention is directed to a process of subbing photographic polyester film comprising election bombard of one side the film and then treating said film side with a subbing composition containing (a) a copolymer latex of a diolefin polymerized with an ethylenically unsaturated monomer and (b) a compound having two or more groups selected from ethyleneimino and methylsulfonyloxy group.

United States Patent [191 Kogure et al.

[451 Sept. 3, 1974 PROCESS FOR SUBBING PHOTOGRAPHIC POLYESTER FILMS [75] Inventors: Motoo Kogure; Yasuji Muroi;

Hideyasu Ohta, all of Tokyo, Japan [73] Assignee: Konishiroku Photo Industry, Co.,

Ltd.

[22] Filed: May 23, 1973 [21] Appl. No.: 363,051

[30] Foreign Application Priority Data May 30, 1972 Japan 47-52978 [52] US. Cl. 117/47 A, 96/87 R [51] Int. Cl... G03c 15/00, G03c 17/00, C23d 3/00, B44d 1/092, B44d 1/52 [58] Field of Search 96/84 R, 87 R; 117/47 A [56] References Cited UNITED STATES PATENTS 2,964,404 12/1960 Burness ..96/87R Caldwell t. Carroll, Jr. et

Primary ExaminerRonald H. Smith Assistant Examiner-J. F. Brammer Attorney, Agent, or Firm-Waters, Roditi, Schwartz & Nissen [5 7] ABSTRACT 3 Claims, No Drawings PROCESS FOR SUBBING PHOTOGRAPHIC POLYESTER FILMS This invention relates to a process for subbing a photographic polyester film in order to have strong adhesion of a photographic gelatinous composition to the polyester film. More particularly, the invention pertains to a process for subbing a photographic polyester film in order to firmly adhere to the polyester film a photographic gelatinous composition, e.g., a gelatinsilver halide emulsion, a gelatinous composition containing an antihalation agent, or a gelatin backing composition, which comprises subjecting at least one side of the polyester film to electron bombardment, and

then applying a subbing composition containing a copolymer latex composed mainly of butadiene or the like diolefin and a certain compound to the treated side of the polyester film.

l-leretofore, various processes have been known as to the subbing of polyester film. According to these known processes, however, it is very often that a photographic gelatinous composition cannot be firmly adhered to the polyester film unless a swelling or dissolving agent for the polyester film is used, because the polyester film is crystalline and hence is highly hydrophobic. When a subbing composition containing such swelling or dissolving agent is coated on a polyester film, however, the support is disadvantageously injured in flatness during the subbing step, and the swelling or solubilizing agent remains not only after drying of the subbing composition but even after coating and drying of a photographic gelatinous composition, to degrade the commercial value of the resulting photographic material due to the unpleasant odor of said swelling or solubilizing agent. Furthermore, many drawbacks have been brought about in the safety and sanitation of the subbing operation due to the vaporization of said swelling or solubilizing agent. For the above reasons, there has been desired the provision of a process for subbing a polyester film so as to firmly adhere a photographic gelatin composition to the polyester film without using no such swelling or solubilizing agent for polyester.

An object of the present invention is to provide a process for subbing a polyester film in which no swelling or solubilizing agent for polyester is substantially used.

Another object of the invention is to provide a process for subbing a photographic polyester film without injuring the polyester film in flatness, which process makes it possible to firmly adhere a photographic gelatinous composition to the polyester film and does not give any detrimental influence to the photographic properties of said photographic gelatinous composition.

Now, we have found that the above-mentioned objects of the present invention can successfully be accomplished according to a process for subbing a polyester film which comprises subjecting at least one side of the polyester film to electron bombardment so that the contact angle thereof with water becomes less than 58, and then applying to the treated surface of the polyester film a subbing composition containing (a) a copolymer latex of a diolefin with other polymerizable ethylenically unsaturated monomer and (b) a compound having two or more of groups selected from ethyleneimino and methylsulfonyloxy groups. If any one of the conditions required in the said subbing proscribed later.

The polyester film used in the present invention is composed of an aliphatic diol and an aromatic dicarboxylic acid, and a typical example thereof is a polyethylene terephthalate film.

The copolymer latex used in the present invention is composed of a diolefin and other polymerizable ethylenically unsaturated monomer. Examples of the diolefin include butadiene, 2-chloroprene, isoprene, neoprene and 2,3-methylbutadiene, and examples of the said other polymerizable ethylenically unsaturated monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, chloroethyl acrylate, chloroethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, glycidyl acrylate, glycidyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, chloromethyl acrylate, chloromethyl methacrylate, 4-chlorobutyl acrylate, 4-chlorobutyl methacrylate, N,N-diethyl acrylate, N,N-diethyl methacrylate, sulfopropyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, acrylamide, methac rylamide, N-alkyl acrylamides (the alkyl includes, for

example, methyl, ethyl, propyl, butyl, amyl and hexyl), N,N-dialkyl acrylamides (the alkyl includes, for example, methyl, ethyl, propyl, butyl and amyl, and the two alkyls may be same or different), Nphenyl acrylamide, N-benzyl acrylamide, N-phenylethyl acrylamide, N- methylol acrylamide, N-hydroxyethyl acrylamide, N,N- dihydroxyethyl acrylamide, N-hydroxycarbonyl methyl acrylamide, N-hydroxycarbonyl ethyl acrylamide, N- hydroxycarbonyl phenyl acrylamide, acrylonitrile, methacrylonitrile, a-chloroacrylonitrile, alkyl a-chloroacrylates and a-chloromethacrylates (the alkyl includes, for example, methyl, ethyl, propyl, butyl, benzyl and cyclohexyl), acrolein, methacrolein, vinyl isocyanate, isopropyl isocyanate, styrene, a-methylstyrene, p-chloromethylstyrene, m-chloromethylstyrene, ochloromethylstyrene, vinyl methyl ether, vinyl ethyl ether, vinyl acetate, vinyl propionate, vinyl chloroacetate, vinyl trichloroacetate, acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid mono-methyl ester, itaconic acid monoethyl ester, maleic anhydride, maleic acid monoalkylesters (the alkyl includes, for example, methyl, ethyl, propyl, amyl, hexyl, pentyl, octyl and benzyl), fumaric acid monoalkyl esters (the alkyl is identical with that of the maleic acid monoalkyl esters) and crotonic acid. These may be used either singly or in combination of two or more.

The above-mentioned copolymer lattice can be easily obtained as commercially available products. Typical examples of the obtainable copolymer lattice are Hycar 2570x5, Hycar 1551, Hycar 1561, Hycar 1571, Hycar 1562, Hycar 1577, Nipol 4850, Nipol LX-l l0, Hycar LX-204, Hycar LX-303, Hycar LX-407, Hycar LX- 411, Hycar LX-4l5, Hycar LX-4l6, Hycar 2507 and Hycar 2518 produced by Nippon Geon Co.; Croslene SA-20, Croslene NA-lO, Croslene NS-16, Croslene 2M-30, Croslene NA-ll, Croslene SA-22, Croslene SA-23, Croslene SA-24, Croslene 2M-33, Croslene 2M-33A, Croslene 2M-36, Croslene 2M-38 and Croslene SK-SO produced by Takeda Chemical Industries, Ltd.; Dow Latex 810, SB Latex No. 612 and SB Latex N0. 632 produced by Asahi Dow Co.; Polylac A1-9l 1, Polylac ML-508, Polylac ML-520, Polylac ML-501, Polylac ML-707, Polylac ML-505, Polylac ML-577 Polylac ML-264 and Polylac SL-204 produced by Mitsui Toatsu Co.; Nitrex 2616, Naugatex 2752B, Naugatex 2001, Naugatex J-9049, Naugatex 2714 and SN- 304 produced by Sumitomo Naugatak Co.; Binder No. 811 and Binder LF-3 produced by Dainichi Seikako Co.; NK Binder SM-200R produced by Nakamura Kagaku Co.; Corporex No. 1001 and Corporex No. 1031 produced by Mitsubishi Gas Kagaku Co.; Wool Cement 3C and Wool Cement No. CS produced by Kyoritsu Kagaku Sangyo Co.; and Bortex GV produced by Meisei Kagaku Co., and all of these are effectively usable.

The copolymer latex used in the present invention is preferably one'which contains 25 to 75 percent by weight of a diolefin and about to 30 percent by weight of a polymerizable ethylenically unsaturated monomer containing at least one reactive active or readily reactive) functional group having at the terminals at least one of hydroxyl, formyl, carboxyl, amido, alkoxy, isocyanato and ethyleneimino groups.

Typical examples of the compound having two or more groups selected from ethyleneimino and methylsulfonyl groups are as follows:

(1)... CH; /CH;

/NCONH(CH2)11NHCON\| CH: CH:

(wherein n is an integer of 1 to NCONH- CH1 CH, NHC ON (3).-- CH; CH,

/NCON\ CH: H2

(4)... CE: OH,

I NCO(OH7):|CON\} C 2 CH:

(wherein n is an integer ol 1 to 10).

(5)...- CH2 CH1 NCOI(OH1)nOCON\ CHz H1 (wherein n is an integer 012 to 6).

(6)--. CH1 CH1 (wherein 71 is an integer of 1 to 4).

p 4 v Cg: /OH,

N\ C H: CH, C: N=C CH 5 CH7 CH1 Cg: /N\ /CH:

if? i \l 1O CH7 N N CH;

CHg-CH; (10).- CH: N\ /CH:

W C 7 N\ /N CH:

(11)... CH: N CH:

1 r il (3E7 /N CHI (I3 OCH!) CH; N CE;

W? T 3Q C N\ /N CH:

(i1 ONE.

(13)" 5 N-o n-mmonnmrr-p -N C C N N O 1 l CQQCH; GHQ-0H1 (wherein n is an integer of 2 to 8).

4) CH i\ or, g

OH I or,

7)-- CH v (i\ Q,

/NCH(CH2) nC H-N on, on H on,

(wherein 7L is an integer of 1 to 6).

S OIN (wherein n is an integer of 1 t 3).

(wherein n is an integer of 2 to 6) (wherein n is an integer of 2 to 200) CHaS O;CH gCH;N-CH:CHO S OgCHa OH O SOgCHa H0 S01CH3 H O SOQCH! CH O S OrCHa CH:(CH:) r-( CHaO S 02GB! 011,0 s 020111 (wherein n is an integer of 0 to 4).

The above-mentioned compound, which is the aforesaid component (b), is used in an amount within the range from 0.01 to 100 percent, preferably from about 0.1 to 30 percent, by weight based on the weight of the aforesaid copolymer latex. Generally, the compound as the component (b) is dissolved in water or an organic solvent or in a mixture of the two, and then added to the aforesaid copolymer latex to prepare a subbing composition. Accordingly, the subbing composition is in the form of an aqueous dispersion, in general, but may alternatively be used, depending on the kind of drying means employed, in the form of a dispersion in a mixed solvent comprising water and methanol, ethanol, acetone or the like organic solvent lower in boiling point than water. In the latter dispersion, the organic solvent is used in 0.1 to 10 times the amount of waters The subbing composition is applied by such means as coating and drying onto the surface of polyester film whose contact angle with water has brought to less than 58 according to electron bombardment. As is well known, the electron bombardment is carried out by use of such corona discharge apparatus or the like that electrons are discharged at a high speed between at least a pair of electrodes in the presence of a gas or under pressure. The electron bombardment should be conducted to such an extent that the contact angle of polyester film with water becomes less than 58. If the contact angle is more than the said value, no satisfac-' tory subbing effect can be attained, as is clear from the working examples described later.

According to the present invention, at least one side of a polyester film is subjected to electron bombardment so that the contact angle thereof with water becomes less than 58", and then a subbing composition containing the aforesaid component (a) (copolymer latex) and the aforesaid component (b) (exemplified compound) is applied according to such means as, for example, coating and drying to the treated side of the polyester film, whereby the subbed polyester film surface becomes highly adherent to a photographic gelatinous composition and sufficiently maintains the excellent adhesion even under severe conditions. Further, the subbing composition according to the present invention does not give any detrimental influence to the photographic properties of photographic gelatinous composition and, moreover, does not require the use of swelling or dissolving for polyester to make it possible to overcome various problems derived from the use of said agents.

The subbing composition used in the present invention may contain various photographic additives in addition to the aforesaid components (a) and (b). For example, the subbing composition may be incorporated with such a hardener used to enhance the water resistance of photographic gelatinous composition as, for example, formaldehyde, mucochloric acid, acrolein, glyoxal, divinyl sulfone, vinyl sulfone, dichlorotriazine, hexahydrol ,3,5-triacryloyl-s-triazine, dihydroxybenzene, methylenebis acrylamide, dicarboxylic acid dinitrophenyl ester, dicarboxylic acid dichloromethyl ester, carbodiimide derivative, Woodwards reagent or chromium chloride. Further, the subbing composition may be incorporated with a surface active agent, e.g., natural saponin or anionic or nonionic synthetic surface active agent, in order to disperse the copolymer latex, and with a matting agent, e.g., colloidal silica, titanium oxide, zinc oxide, aluminum oxide polymethyl methacrylate or polystyrene beads, or starch powder. Still further, the subbing composition may be incorporated with dye or pigment for antihalation or for coloration of film base.

The present invention is illustrated in more detail below with reference to examples, but the scope of the invention is not limited to these.

Example I were individually treated under such conditions as shown in Table l by use of a corona discharge apparatus (Lepel HFSG-Model 2). Subsequently, the treated surface of each film was coated with a subbing composition comprising 6 g. of Polylac SL-204 (produced by Mitsui Toatsu Co.), 0.18 g. of hexamethylenebis ethyleneimino ureide (the exemplified compound (1), wherein n==6), 30 cc. of water and 70 cc. of methanol, and then dried at 120C. for 1 minute to form a sub layer. The thus formed sub layer was coated with a litho type photographic emulsion containing silver chlorobromide and then dried to obtain a sample. Each sample thus obtained was subjected to the film adhesion tests described below to obtain the results as set forth in Table 1. Dry film adhesion test: invention The photographic emulsion layer surface of each sample was scratched with a razor so as to form squares. Subsequently, a cellophane adhesive tape was applied under finger pressure onto the said surface and then quickly stripped off therefrom, and the residual ratio of the photographic emulsion layer on the film base to the adhesion surface area of the tape was repre sented by percentage. Wet film adhesion test:

In a treating bath, the photographic emul emulsion layer surface of each sample was scratched with the sharp tip of a gimlet so as to form squares and then rubbed, and the residual ratio of the photographic emulsion layer on the film base was represented by per centage.

Table 1 From Table I, it is .understood that the samples (1) to according to the present invention were well adherent to the litho type photographic emulsion. Further, no problem was observed in the photographic properties of the samples according to the present invention.

Example 2 A biaxially stretched polyethylene terephthalate film, which had been subjected to corona discharge treatment under the same conditions as in the case of the sample (3) prepared in Example 1, was coated with a subbing composition comprising 8 g. of Naugatex SN- 304 (produced by Sumitomo Naugatak Co.), 0.8 g. of trimethylenedimethane sulfonate (the exemplified compound (24), wherein n=3), 90 cc. of water and cc. of methanol, dried at 110 C. for 1 minute, further coated with a roentgen emulsion containing silver iodobromide and then dried to prepare a sample (7).

For comparison, a biaxially stretched polyethylene terephthalate film was pre-treated with a methanol solution containing p-chlorophenol, dried at 80 C. for 2 minutes, and then equally divided into two. One film was coated with the above-mentioned subbing composition, and the other film was coated with the same composition as above, except that the trimethylenedimethane sulfonate was not contained. These films were individually coated onto the subbed surfaces with the same roentgen emulsion as above, and then dried to prepare samples.

The samples thus prepared were subjected to the same film adhesion tests as in Example I to obtain the results as set forth in Table 2.

From Table 2, it is understood that the sample (7) according to the present invention was well adherent to the roentgen emulsion, and the subbing effect was entirely unsatisfactory when the pre-treatment was conducted by use of solvent. In case the sample 7) was coated with the subbing composition containing no trimethylenedimethane sulfonate, the dry film adhesion was percent and the treated sub layer adhesion was 60 percent and thus was unsatisfactory.

Example 3 Biaxially stretched polyethylene terephthalate films which had been subjected to corona discharge treatment under the same conditions as in the case of the sample (1) prepared in Example 1, were individually coated onto the surfaces with each of such subbing compositions as shown in Table 3, dried at C. for 1 minute, further coated with an antihalation backing gelatin layer containing an absorption dye, and then dried to prepare samples. These samples were subjected to the same sub layer adhesion tests as in Example l to obtain the results as set forth in Table 3.

From Table 3, it is understood that the samples l0) and (l 1) according to the present invention were well adherent to the colored backing layer.

Example 4 A biaxially stretched polyethylene terephthalate film, which had-been subjected to corona discharge treat- .ment under the same conditions as in the case of the Table 3 Sample Subbing composition (made I ccv Dry film Wet film No. by addition of water) adhesion adhesion (I0) Hycur 2570X5 (7 g.)

I00 I00 Exemplified compound I4) (02 g.) (ll) Croslene 2M-38 (10 g.)

I00 I00 Exemplified compound (30) l g.) (l2) Hycur 2570X5 (7 g.) I00 (I3) Croslene 2M-38 (10 g.)

I00 40 Glyoxal (0.2 g.) l4) Vinylsol" (Acid-modified acrylic acid ester (5 g.) copolymer produced by Duido Kasei Co.)

0 100 Exemplified compound l4) (0. l5 g.) (l5) Nikusol A-ZO" (Selfcrosslinking type (5 g.) acrylic resin produced by Nippon Carbide Co.)

0 40 Mucochloric acid (0.3 g.)

What we claim is: 2. A process for subbing a photographic polyester 1. A process for subbing a photographic polyester film as claimed in claim 1, wherein said compound (b) film which comprises subjecting at least one side of the is that which at least one ethyleneiginqgroup in addipolyester film to electron bombardment so that the tion to one or more groups selected from contact angle thereof with water becomes less than 58, ethyleneimino and methylsulfonyloxy groups.

and then applying to the treated side of the film a sub- .3. A process for subbing photographic polyester film bing composition containing (a) a copolymer latex of as claimed incl aim l, wherein said compound (b) is a diolefin with other polymerizable ethylenically unsatthat whi h at lea t ne methylsulfonyloxy group in adurated monomer and (b) a compound having two or dition to one or more groups selected from more groups selected from ethylenermino and methylthyl i in and methylsulfonyloxy groups. sulfonyloxy groups. 

2. A process for subbing a photographic polyester film as claimed in claim 1, wherein said compound (b) is that which at least one ethyleneimino group in addition to one or more groups selected from ethyleneimino and methylsulfonyloxy groups.
 3. A process for subbing photographic polyester film as claimed in claim 1, wherein said compound (b) is that which at least one methylsulfonyloxy group in addition to one or more groups selected from ethyleneimino and methylsulfonyloxy groups. 